Process of recovering hydrocarbon oils and other byproducts from oil shale and the like



Marcb17, 1942. H co Ds -r 2,276,342

PROCESS OF RECOVERINO HQDROCARBON OILS AND OTHER BYPRODUCTS FROM OIL-SHALE AND THE LIKE Filed Oct. 18, 1937 l/ CONDEMSER ,INVENTORS E. H. HEcORQS ATTORNEYS .practical value. ment, utilizing comparatively low pressures and UNITED STATES PATENT OFFICE PROCESS BON OILS FROM OIL AND OF rmcovamuc nrnnooaa OTHER BYPRODUCTS SHALE AND r m LIKE Elmer 11. Records and James E. Louttit, Tacoma,

Wash.; said Louttit assignor to said Records Application October 18, 1937, Serial No. 169,594

'8 Claims.

This invention deals with the art of recovering hydrocarbon oils and other valuable byproducts from oil, shale, bituminous sands and like raw materials, and

to a novel process utilizing superheated steam solely as the heating medium and wherein vital chemical reactions addition to the shale, sands or other material under distillation, of

certain solid, liquid or gaseous materials that are high in hydrocarbons of a desired nature, whereby to increase the yield of hydrocarbon oils and low boiling oils of value;

it being the principal object of this invention .to provide a process that is an improvement upon the generally used recovering processes and which leads to the recovery of a greater quantity it has reference more particularly and a superior quality of products and byproducts than heretofore has been possible.

Explanatoryv to the present invention, it will here be stated classified as pyrobitumens, and these, upon dethat the organic matter that makes up the hydrocarbon oils in oil shale are structive distillation, yield oils of various character which have green oil. complex molecule, which, of

been termed Kerogen or itself, has little The'present process, or treatmoderate heat, has for an object and provides for the recovery of these oils in a cured or refined condition. At the same time; the reaction is supplied with vital and necessary compounds so that reformation in a single operation increases the yield of valuable hydrocarbon oils and the pro- Kerogen, as such, has a large and hydrocarbons being used because they supply a continuous flow of such evolving vapors and'require approximately the same length of time for destructive distillation as is required by the oil shale.

The destructive distillation of the coal or lignite in the base of the retort resu ts in a considerable evolution of gases containing hydrogen.

This hydrogen, upon combining with the decomposed kerogen, results in a high degree oi saturation of the resulting compounds.

In accordance with the present process, superheated steam at temperatures ranging from 700 F. to 1800 F. and at pressures from atmospheric to fifty pounds is ,used. Under the conditions of this process, the superheated steam as the sole heating medium is desirable because of its high specific heat and active hydrogen and oxygen content with the absence of inert gases, and anotheradvantage in its use'is that heat carried into the mass by the superheated steam is uniformly distributed, and although the temperatures are controlled so that decomposition of the shale takes place, there are no hot walls or zones of sufficient temperature to allow cracking of the final vaporous products formed in the final reaction. This has resulted in amaterial decrease in the length of time of treatment encountered in other methods or processes. Furthermore, it has been found that theincreased yield of hydrocarbon oil is due to the enrichening effect of the reactions of the process and that such oils are much easier refined and a decrease in refinery losses results therefrom.

In the accompanying drawing, there is illustrated diagrammatically an improved apparatus for carrying out the present process, and in this drawing, 1 designates, in the entirety, the reaction retort; 2, a condenser; 3, a decanter; and 4, the steam superheater. The reaction retort l coinprises a cylindrical vessel preferably built of steel boiler plate and comprising-an outer shell 10 and an inner shell ll of lesser diameter. These are coaxially disposed, to provide an intermediate, annular space or expansion chamber l6, and at their lower ends are welded together as at 5 to form a gas-tight joint and are drawn inwardly to form a throat leading to an outlet or opening l2 of restricted diameter. On the inside face of the inner shell II at the beginning. of the throat or restricted portion, vertically spaced baffle rings I3 and I4 are welded within the shell. baflles are spaced from the walls of the shell for the purpose of deflecting the discharging residue toward the axial center, and also to serve as protective guards overlying a plurality of ports 15 which open through the shell H from the intermediate space IG, or expansion chamber, into the reaction chamber.

.At its upper .end, the edge of the shell I!) is turned inwardly and is welded to .the inner shell .The lower edges of 'these i the method of use ing from the superheater 4 into the upper end of the expansion chamber H5, and the flow of steam Fitted over the upper end of the shell I I, which extends somewhat above the shell l and expansion chamber 16, is a closure or lid H! which is seated in a' held clamped in and a jack screw gage the lid. t

Upon removal of the lid, the reaction be'r is opened for place by a cross clamp bar 2| mounted on the bar to enfrom the reaction chamber into the condenser. At its inner end, the pipe 22 terminates near or at the center of the reaction chamber, and is provided at that endwith a T-fitting 24, having the cross head portion disposed in a vertical action chamber, through the opening l2 at the lower end thereoffalls into a quench chamber D. The opening I! is provided with a gas-tight dis- I9 is removed and the charged with spent or zone which is designated Over this zone C, the required amount of coal or lignite is charged to fill the zone designated within the bracket B. Then broken oil shale is charged into the main part of the reaction chamber to near the upper end, thus filling the zone designated within the bracket A. The charging thus being completed, the lid I4 is clamped in place and tightened with the bar and jack screw provide In the meantime, superheated steam has been provided in superheater 4 at the temperatures pletion of the of the open chain and pressures required. opened, allowing the superheated intothe expansion chamber volatiles contained in the coal rise through the shale mass, they, in combination with other released gases from the steam and shale, reform into hydrocarbon molecules of gaseous, and liquid nature. These are thoroughly mixed by turbulence in the upper portion of the reaction chamber, and pass out through the T-fitting 24, pipe 22 and valve 31, which has been opened, and enter the condenser 2 which may be of an air cooled or water cooled type.

The condensed hydrocarbons and steam then At proper intervals, oily hydrocarbons stored in the pressure tank 26 may, upon opening a valve 21' on pipe 21, be injected under pressure into the-distilling mass through pipes 21 and 28. This period of treatment varies with the type of oil shale used, but it has been found that this process will take considerably less time of reaction than that required by processes that resort to external heatingmethods. Upon comproper treatment, then the valve or valves [8 are closed, as is also the valve 31.

' trap 33 is then opened and and may be carried thereby to waste.

In drawing the charge, it is desirable, however, to leave enough of the spent shale'of zone A in her similar to that described above.

In the use of super-heated steam, it has been eral operation will be approximately 1200 F., but it has been found that the exothermic and endothermic cycles of the reacting mass, from 700 to 1800 F. may be necessary. In no case should the temperature be so great that secondary reactions predominate.

It has been found by the present method of processing that" a much 'larger proportion of paraflin hydrocarbons are formed having the general formula CzH2n+2; such paraflins being or saturated type. It has alin order to take adso been found that there is a higher proportion of saturated monocyclic or .naphthene series of compounds of the general formula CnHiln; these being of ring or closed chain type.

These types of saturated compounds are very desirable as they are easily converted into motor fuel of high anti-knock rating as well as a lubricating oil and wax of value; The yield of such motor fuel is thus greater than that ordinarily obtained from oil shale by simple destructive distillation.

The foregoing description is intended to be illustrative of the process and of an apparatus for practising it, and it is not intended that it shall in any way be restrictive, but that the invention described shall be liberally construed in accordance with the claims appended hereto, and in construing these claims it is desired that the word cal" shall apply equally to coal, lignite or other carbonaceous materials capableof the same results, while oil-shale" shall be understood to be any of the various oil-shaies, bituminous sands and like raw materials capable of the uses hereinexplained in connection with this process.

Having thus described our invention, what we claim as new therein and desire to secure by Letters Patent is:

1. The process of recovering hydrocarbon oils and gases from oil-shale which comprises en-' introducing superheated closing a mass of oil-shale in a reaction retort upon a base of coal, then passing superheated steam through the coal and oil-shale to effect decomposition thereof and in a manner whereby the decomposition products fromthe coal pass through the mass of oil-shale and finally withdrawingand condensing the said products.

2. The process of recovering hydrocarbon oils and gases from oil-shale which comprises enclosing a mass of oil-shale in a reaction retort upon a base of coal, then passing superheated steam at a. temperature'of not less than-700 F. and pressure of not over fifty pounds through the coal and oil-shale t'o 'eifect decomposition thereof and in a manner whereby the decomposition products from the coal pass through the mass of oil-shale and finally withdrawing and condensing the said products.

3. The process of recovering hydrocarbon oils and gases from oil-shale comprising enclosing a mass of oil-shale in a reaction retort upon a layer of coal, passing superheated steam upwardly through the coal and oil-shale to eiiect decomof coal, heating the coal and oil-shale with a stream of superheated steam passed upwardly therethrough and mixing the evolved vapors in a space in the reaction retort above the mass of shale, then withdrawing and condensing the vapors. I

5. The processor producing combustible gas comprising enclosing a mass of oil-shale and'a quantity of coal in a closed reaction chamber,

steam as a reaction medium, and causing the evolved gases to mix without cracking. v 6. The process of producing hydrocarbon .oils and gases from oil-shale, comprisingsimuitaneously decomposing oil-shale and coal in a closed reaction chamber by the use of superheated steam as the heating medium and recombining themolecules of the hydrocarbon vapors so formed by the enricheni'ng and saturating gases and vapors of the distilled coal. I

7. A process of producing hydrocarbon oils andgases from oil-shale by subdividing a small layer of coal or lignite insuch a manner that decomposition products from such coal pass upward. through a mass of oil-shale in a'closed reaction chamber; passing superheated steam through the coal and shale as the sole reducing medium. said superheated steam to be not less than 700 F and at apressure not over 50 pounds; and spraying volatile hydrocarbon oil into a reaction zone in the lower part of said oil-shale in such a manner that the uprising superheatedsteam will react upon such liquid hydrocarbon and that the gases so formed may rise and combine with the volatile products of the decomposing oil-shale and coal.

8. A process which comprises the decomposition of a mass or oil-shale and a thin bed of coalor lignite, and a small stream of a volatile hy- 

